Extended drain diesel lubricant formulations

ABSTRACT

An additive concentrate, lubricant composition, and method of operating a diesel engine on the lubricant composition wherein the lubricant composition exhibits extended service life. The concentrate and lubricant composition include a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition, and an antioxidant selected from hindered phenolic derivatives of C 3  to C 6  acids and C 7  to C 9  esters of hindered phenolic derivatives of C 3  to C 6  acids. The lubricant composition is substantially devoid of zinc dialkyldithiophosphate compounds.

TECHNICAL FIELD

The disclosure relates to lubricant formulations for diesel engine applications and in particular to lubricant formulations that exhibit reduced lead uptake in Group I and Group II base oils that contain catalytic copper compounds thereby improving the drain interval for the lubricant compositions.

BACKGROUND AND SUMMARY

Lubricant formulations for diesel engine applications, particularly medium speed diesel (MSD) engines such as used in railroad applications in severe duty service have to be changed routinely over a relatively short period of time. A typical MSD engine oil is commonly changed after about 184 in service days. It is believed that small amount of oil soluble copper corrosion products, typically from the engine oil coolers, may accumulate in the lubricant to the point that the copper causes catalytic oxidation of the oil which causes an increase in the lead in the lubricant. Accordingly, to prevent the oxidation of oil components, oxidation inhibitors are added to the lubricant. However, conventional oxidation inhibitors are effective in the presence of copper for only a short period of time. Hence, the lubricant service life is significantly shortened. There is a need therefore for a lubricant formulation that is effective to increase the service life (drain interval) of the lubricant even in the presence of copper corrosion products so that oxidation of the oil and corrosion of lead components in the engine is minimized.

With regard to the foregoing, embodiments of the disclosure provide an additive concentrate, lubricant composition, and method of operating a diesel engine on the lubricant composition wherein the lubricant composition exhibits extended service life. The concentrate and lubricant composition include a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition, and an antioxidant selected from hindered phenolic derivatives of C₃ to C₆ acids and C₇ to C₉ esters of hindered phenolic derivatives of C₃ to C₆ acids. The lubricant composition is substantially devoid of zinc dialkyldithiophosphate compounds.

In one embodiment, the disclosure provides a lubricant composition for a diesel engine. The lubricant composition has therein a major amount of oil of lubricating viscosity, a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition, and a minor amount of an antioxidant additive selected from hydroxy phenyl acids and hydroxy phenyl esters of the formula:

wherein each R¹ is a primary, secondary or tertiary alkyl group having from 3 to 6 carbon atoms and R² is selected from the group consisting essentially of C₃ to C₆ acids and C₇ to C₉ esters of the C₃ to C₆ acids. The lubricant composition is substantially devoid of zinc dialkyldithiophosphate compounds.

Another embodiment of the disclosure provides an additive concentrate for a diesel engine lubricant. The additive concentrate has therein a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the additive concentrate, and an antioxidant selected from hydroxy phenyl acids and hydroxy phenyl esters of the formula:

wherein each R¹ is a primary, secondary or tertiary alkyl group having from 3 to 6 carbon atoms and R² is selected from the group consisting essentially of C₃ to C₆ acids and C₇ to C₉ esters of the C₃ to C₆ acids. A lubricant composition including the additive concentrate is substantially devoid of zinc dialkyldithiophosphate compounds.

Yet another embodiment of the disclosure provides a method for extending a drain interval for a lubricant for a medium speed diesel engine. The method includes supplying as the lubricant, a lubricant composition having a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition, and an antioxidant selected from hindered phenolic derivatives of C₃ to C₆ acids and C₇ to C₉ esters of hindered phenolic derivatives of C₃ to C₆ acids. The lubricant composition is substantially devoid of zinc dialkyldithiophosphate compounds. An engine is operated on the lubricant composition for an extended period of time between lubricant drain intervals.

An advantage of the disclosed embodiments is that drain intervals for lubricants used in diesel engines, such as medium speed diesel engines used for railroad applications, may be significantly extended even in the presence of copper corrosion products that may catalyze oxidation of the lubrication oil and damage engine components. For example, a 50% increase in the drain interval for such lubricant, even in the presence of copper ion corrosion products, is very desirable and may significantly reduce oil and maintenance costs for operating such engines. Another advantage of the disclosed embodiments is the unexpected reduction of lead corrosion and the extension of oxidation control provided by the particular oxidation inhibitor described herein as compared to conventional oxidation inhibitors. Other benefits and advantages of the compositions and methods described herein may be found in the following detailed description and examples.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features, aspects, and advantages of the present disclosure may be better understood by reference to the following detailed description, appended claims, and accompanying figures, wherein like reference characters indicate like elements throughout the several views, and wherein:

FIGS. 1 and 2 are graphic illustrations of lead uptake of lubricants containing additive formulations made with Group I and Group II base oils with and without added copper ions compared to the lead uptake of a lubricant containing a reference additive with and without added copper ions.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

As the industry moves toward the use of low SAP (low sulfated ash and phosphorus) lubricant compositions, the challenge has been to provide lubricants that not only meet the low SAP criteria but also provide enhanced protection of engine components. A particularly difficult lubricant application is present for heavy duty diesel engines and medium speed diesel engines operating in severe duty service. Such lubricants are susceptible to the oxidation of oil components of the engine. However, as described in more detail below, the compositions of the disclosed embodiments including certain antioxidant additives may be effective to reduce the oxidation of oil components over extended periods of time thereby extending the life of the lubricant even in the presence of soluble copper ions.

For the purposes of this disclosure, the term “hydrocarbon soluble” means that the compound is substantially suspended or dissolved in a hydrocarbon material, as by reaction or complexation of a reactive metal compound with a hydrocarbon material. As used herein, “hydrocarbon” means any of a vast number of compounds containing carbon, hydrogen, and/or oxygen in various combinations.

The term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

-   -   (1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or         alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)         substituents, and aromatic-, aliphatic-, and         alicyclic-substituted aromatic substituents, as well as cyclic         substituents wherein the ring is completed through another         portion of the molecule (e.g., two substituents together form an         alicyclic radical);     -   (2) substituted hydrocarbon substituents, that is, substituents         containing non-hydrocarbon groups which, in the context of the         description herein, do not alter the predominantly hydrocarbon         substituent (e.g., halo (especially chloro and fluoro), hydroxy,         alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);     -   (3) hetero-substituents, that is, substituents which, while         having a predominantly hydrocarbon character, in the context of         this description, contain other than carbon in a ring or chain         otherwise composed of carbon atoms. Hetero-atoms include sulfur,         oxygen, nitrogen, and encompass substituents such as pyridyl,         furyl, thienyl and imidazolyl. In general, no more than two,         preferably no more than one, non-hydrocarbon substituent will be         present for every ten carbon atoms in the hydrocarbyl group;         typically, there will be no non-hydrocarbon substituents in the         hydrocarbyl group.

Oxidation Inhibitor Components

An important component of the lubricant compositions described herein is one or more oxidation inhibitors. At least one of the oxidation inhibitors in the lubricant composition may be selected from phenolic derivatives of C₃ to C₆ acids and C₇ to C₉ esters of phenolic derivatives of C₃ to C₆ acids. For example, the oxidation inhibitor may be a compound of the formula:

wherein each R¹ is a primary, secondary or tertiary alkyl group having from 3 to 6 carbon atoms and R² is selected from the group consisting essentially of C₃ to C₆ acids and C₇ to C₉ esters of the C₃ to C₆ acids. Specific examples of the foregoing antioxidant component may include one or more of di-alkyl hydroxyphenyl alkanoic acid and di-alkyl hydroxyphenyl alkanoic acid ester. A particularly suitable antioxidant compound may be selected from di-tertiary alkyl hydroxyphenyl C₃ to C₆ alkanoic acid and C₇ to C₉ esters thereof. In one embodiment the antioxidant compound comprises 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid. In another embodiment, the antioxidant compound comprises 3-(3,5-di-tert-butyl-4-hydroxyphenyl)hydrocinnamic acid, C₇-C₉ branched alkyl esters. The foregoing oxidation inhibitors may be used in an amount in a lubricant composition that is effective to extend the lubricant drain interval to greater than about 200 “in-service” days. “In-service” days refers to the actual days of use of an engine containing the lubricant. For example, amounts may range from about 0.5 to about 10.0 weight percent based on a total weight of a fully formulated lubricant composition. It is particularly desirable to include at least about 0.8 weight percent or greater of the foregoing antioxidant in the lubricant composition, based on a total weight of the lubricant composition. Other suitable amounts of the foregoing antioxidant compound may range from about 1.0 weight percent to about 5.0 weight percent based on a total weight of the lubricant composition.

Other antioxidants that may be used in combination with the foregoing antioxidant compound include, but are not limited to, diarylamines, alkylated phenothiazines, sulfurized compounds, a molybdenum complex, and ashless dialkyldithiocarbamates.

Diarylamine antioxidants include, but are not limited to diarylamines having the formula:

wherein R³ and R⁴ each independently represents a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms. Illustrative of substituents for the aryl group include aliphatic hydrocarbon groups such as alkyl having from 1 to 30 carbon atoms, hydroxy groups, halogen radicals, carboxylic acid or ester groups, or nitro groups.

The aryl group is preferably substituted or unsubstituted phenyl or naphthyl, particularly wherein one or both of the aryl groups are substituted with at least one alkyl group having from 4 to 30 carbon atoms, preferably from 4 to 18 carbon atoms, most preferably from 4 to 9 carbon atoms. It is preferred that one or both aryl groups be substituted, e.g. mono-alkylated diphenylamine, di-alkylated diphenylamine, or mixtures of mono- and di-alkylated diphenylamines.

The diarylamines may be of a structure containing more than one nitrogen atom in the molecule. Thus the diarylamine may contain at least two nitrogen atoms wherein at least one nitrogen atom has two aryl groups attached thereto, e.g. as in the case of various diamines having a secondary nitrogen atom as well as two aryls on one of the nitrogen atoms.

Examples of diarylamines that may be used include, but are not limited to: diphenylamine; various alkylated diphenylamines; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; monobutyldiphenyl-amine; dibutyldiphenylamine; monooctyldiphenylamine; dioctyldiphenylamine; monononyldiphenylamine; dinonyldiphenylamine; monotetradecyldiphenylamine; ditetradecyldiphenylamine, phenyl-alpha-naphthylamine; monooctyl phenyl-alpha-naphthylamine; phenyl-beta-naphthylamine; monoheptyldiphenylamine; diheptyl-diphenylamine; p-oriented styrenated diphenylamine; mixed butyloctyldi-phenylamine; and mixed octylstyryldiphenylamine. When used, the amount of diarylamine antioxidant compound in the fully formulated lubricant composition may range from about 0.05 to about 5.0 weight percent based on a total weight of the lubricant composition. A desirable range of diarylamine antioxidant compound may range from about 0.09 to about 3.0 weight percent based on a total weight of the lubricant composition.

Another class of aminic antioxidants includes phenothiazine or alkylated phenothiazine having the chemical formula:

wherein R⁵ is a linear or branched C₁ to C₂₄ alkyl, aryl, heteroalkyl or alkylaryl group and R⁶ is hydrogen or a linear or branched C₁-C₂₄ alkyl, heteroalkyl, or alkylaryl group. Alkylated phenothiazine may be selected from the group consisting of monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monoctyl-phenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.

The sulfur containing antioxidants include, but are not limited to, sulfurized olefins that are characterized by the type of olefin used in their production and the final sulfur content of the antioxidant. High molecular weight olefins, i.e. those olefins having an average molecular weight of 168 to 351 g/mole, are preferred. Examples of olefins that may be used include alpha-olefins, isomerized alpha-olefins, branched olefins, cyclic olefins, and combinations of these.

Alpha-olefins include, but are not limited to, any C₄ to C₂₅ alpha-olefins. Alpha-olefins may be isomerized before the sulfurization reaction or during the sulfurization reaction. Structural and/or conformational isomers of the alpha olefin that contain internal double bonds and/or branching may also be used. For example, isobutylene is a branched olefin counterpart of the alpha-olefin 1-butene.

Sulfur sources that may be used in the sulfurization reaction of olefins include: elemental sulfur, sulfur monochloride, sulfur dichloride, sodium sulfide, sodium polysulfide, and mixtures of these added together or at different stages of the sulfurization process.

Unsaturated oils, because of their unsaturation, may also be sulfurized and used as an antioxidant. Examples of oils or fats that may be used include corn oil, canola oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, coconut oil, rapeseed oil, safflower seed oil, sesame seed oil, soybean oil, sunflower seed oil, tallow, and combinations of these.

The amount of sulfurized olefin or sulfurized fatty oil delivered to the finished lubricant is based on the sulfur content of the sulfurized olefin or fatty oil and the desired level of sulfur to be delivered to the finished lubricant. For example, a sulfurized fatty oil or olefin containing 20 weight % sulfur, when added to the finished lubricant at a 1.0 weight % treat level, will deliver 2000 ppm of sulfur to the finished lubricant. A sulfurized fatty oil or olefin containing 10 weight % sulfur, when added to the finished lubricant at a 1.0 weight % treat level, will deliver 1000 ppm sulfur to the finished lubricant. It is preferred to add the sulfurized olefin or sulfurized fatty oil to deliver between 200 ppm and 2000 ppm sulfur to the finished lubricant. The foregoing aminic, phenothiazine, and sulfur containing antioxidants are described for example in U.S. Pat. No. 6,599,865.

The ashless dialkyldithiocarbamates which may be used as antioxidant additives include compounds that are soluble or dispersable in the additive package. It is also preferred that the ashless dialkyldithiocarbamate be of low volatility, preferably having a molecular weight greater than 250 daltons, most preferably having a molecular weight greater than 400 daltons. Examples of ashless dithiocarbamates that may be used include, but are not limited to, methylenebis(dialkyldithiocarbamate), ethylenebis(dialkyldithiocarbamate), isobutyl disulfide-2,2′-bis(dialkyldithiocarbamate), hydroxyalkyl substituted dialkyldithiocarbamates, dithiocarbamates prepared from unsaturated compounds, dithiocarbamates prepared from norbornylene, and dithiocarbamates prepared from epoxides, where the alkyl groups of the dialkyldithiocarbamate can preferably have from 1 to 16 carbons. Examples of dialkyl-dithiocarbamates that may be used are disclosed in the following patents: U.S. Pat Nos. 5,693,598; 4,876,375; 4,927,552; 4,957,643; 4,885,365; 5,789,357; 5,686,397; 5,902,776; 2,786,866; 2,710,872; 2,384,577; 2,897,152; 3,407,222; 3,867,359; and 4,758,362.

Examples of suitable ashless dithiocarbamates are: Methylenebis-(dibutyldithiocarbamate), Ethylenebis(dibutyldithiocarbamate), Isobutyl disulfide-2,2′-bis(dibutyldithiocarbamate), Dibutyl-N,N-dibutyl-(dithiocarbamyl)succinate, 2-hydroxypropyl dibutyldithiocarbamate, Butyl(dibutyldithiocarbamyl)acetate, and S-carbomethoxy-ethyl-N,N-dibutyl dithiocarbamate. The most preferred ashless dithiocarbamate is methylenebis(dibutyldithiocarbamate).

Metal Deactivators

Another important component of the lubricant composition according to the disclosure is a metal deactivator component. The metal deactivator component may be selected from thiadiazole and triazole compounds. Examples of thiadiazole compounds include, but are not limited to, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,5-bis-(hydrocarbyldithio)-1,3,4-thiadiazoles. Suitable thiadiazole compounds are the 1,3,4-thiadiazoles, especially 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles wherein the hydrocarbyl group contains from about 12 to about 20 carbon atoms. The thiadiazole compounds may be used in the lubricant composition in amount ranging from about zero up to about 1% by weight based on the total weight of the lubricant composition. A representative suitable amount of the thiadiazole may range from about 0.05 to about 0.5 weight percent based on the total weight of the lubricant composition.

Another metal deactivator component that may be used in lubricant compositions according to the disclosure is the triazole compounds, particularly aminotriazole compounds. The aminotriazole compounds may be selected from hydrocarbyl substituted bis-aminotriazoles for example polyalkenylene bis-aminotriazoles. A particularly suitable hydrocarbyl substituted bis-aminotriazole is a polyisobutenyl-bis-1,2,4-triazole-3-amine. The polyisobutenyl group of the aminotriazole may have a number average molecular weight ranging from 500 to about 5000 Daltons. In another embodiment, the molecular weight of the polyisobutenyl group may range from about 1000 to about 2000 Daltons. For example a molecular weight of the polyisobutenyl group may range from about 1100 to about 1500 Daltons. In yet another embodiment, the polyalkenyl group may be a “highly reactive” polyalkenyl group. The term “highly reactive” means the polyalkenyl group may have at least 20%, particularly at least 50%, and more particularly at least 70% of olefin double bonds located at a terminal position on the carbon chain. The foregoing polyalkenylene bis-aminotriazoles may also exhibit properties such as dispersancy as well as metal deactivation to lubricant compositions.

When used in a lubricant composition in combination with the thiadiazole described above, the lubricant composition may contain at least about 10 times more by weight of the hydrocarbyl substituted bis-aminotriazole than the thiadiazole. For example the lubricant composition may contain from about 10 to about 25 times more by weight of the hydrocarbyl substituted bis-aminotriazoles than of the thiadiazole component of the lubricant composition.

Dispersant Components

Dispersants contained in the lubricant composition according to the disclosure include, but are not limited to, an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed. Typically, the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group. Dispersants may be selected from Mannich dispersants as described in U.S. Pat. Nos. 3,697,574 and 3,736,357; ashless succinimide dispersants as described in U.S. Pat. Nos. 4,234,435 and 4,636,322; amine dispersants as described in U.S. Pat. Nos. 3,219,666, 3,565,804, and 5,633,326; Koch dispersants as described in U.S. Pat. Nos. 5,936,041, 5,643,859, and 5,627,259, and polyalkylene succinimide dispersants as described in U.S. Pat. Nos. 5,851,965; 5,853,434; and 5,792,729. Like the hydrocarbyl substituted bis-aminotriazoles, the hydrocarbyl substituted succinimide dispersants may be selected from succinimide dispersants made with highly reactive polyalkenyl groups. The molecular weight of the polyalkenyl group of the dispersant may range from about 1000 to about 5000 Daltons, for example from 1500 to about 2500 Daltons. The lubricant composition according to the disclosure may contain from about 0.5 to about 10.0 weight percent of the dispersant based on a total weight of the lubricant composition.

Detergent Components

Detergents that may be included in the lubricant composition may include alkaline and alkaline earth metal phenates and/or sulfonates, among others. Such detergents are well known in the art. Examples of suitable detergents may include, but are not limited to, neutral and overbased salts such as a sodium sulfonate, a sodium carboxylate, a sodium salicylate, a sodium phenate, a sulfurized sodium phenate, a lithium sulfonate, a lithium carboxylate, a lithium salicylate, a lithium phenate, a sulfurized lithium phenate, a magnesium sulfonate, a magnesium carboxylate, a magnesium salicylate, a magnesium phenate, a sulfurized magnesium phenate, a calcium sulfonate, a calcium carboxylate, a calcium salicylate, a calcium phenate, a sulfurized calcium phenate, a potassium sulfonate, a potassium carboxylate, a potassium salicylate, a potassium phenate, a sulfurized potassium phenate, a zinc sulfonate, a zinc carboxylate, a zinc salicylate, a zinc phenate, and a sulfurized zinc phenate. Further examples include a lithium, sodium, potassium, calcium, and magnesium salt of a hydrolyzed phosphosulfurized olefin having about 10 to about 2,000 carbon atoms or of a hydrolyzed phosphosulfurized alcohol and/or an aliphatic-substituted phenolic compound having about 10 to about 2,000 carbon atoms. Even further examples include a lithium, sodium, potassium, calcium, and magnesium salt of an aliphatic carboxylic acid and an aliphatic substituted cycloaliphatic carboxylic acid and many other similar alkali and alkaline earth metal salts of oil-soluble organic acids. A mixture of a neutral or an overbased salt of two or more different alkali and/or alkaline earth metals may be used. Likewise, a neutral and/or an overbased salt of mixtures of two or more different acids may also be used.

In one embodiment, the detergent includes a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition or concentrate. The total amount of detergent used in the lubricant compositions according to the disclosure may range from about 0.1 to about 15.0 percent by weight based on a total weigh of the lubricant composition. More particularly, the amount of detergent in the lubricant composition according to the disclosure may range from about 0.5 to about 5 percent by weight based on a total weight of the lubricant composition.

Viscosity Modifiers

Viscosity modifiers (VM) function to impart high and low temperature operability to a lubricating oil. The VM used may have that sole function, or may be multifunctional. Viscosity modifiers may be selected from olefin (co) polymer(s), polyalkyl (meth) acrylate(s), vinyl aromatic-diene copolymers and mixtures thereof. Typically, the viscosity modifier, when used, will be present in an amount of from 0.01 to 20 weight percent, for example from about 1 to about 10 weight percent, based on a total weight of the lubricant composition.

The olefin (co) polymer viscosity modifiers may include at least one homopolymer or copolymer resulting from the polymerization of C₂-C₁₄ olefins and having a number average molecular weight of from 250 to 50,000, for example, from 1,000 to 25,000, as determined by gel permeation chromatography (GPC). The C₂-C₁₄ olefins include ethylene, propylene, 1-butene, isobutylene, 2-butene, 1-octene, 1-decene. 1-dodecene and 1-tetradecene. Suitable (co) polymers include polypropylene, polyisobutylene, ethylene/propylene copolymers, ethylene/butene copolymers and 1-butene/isobutylene copolymers. The ethylene content of the olefin copolymers is generally from about 35 to about 65, and desirable from about 40 to 60, weight percent.

Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.

Functionalized olefin copolymers that may be used include interpolymers of ethylene and propylene which are grafted with an active monomer such as maleic anhydride and then derivatized with an alcohol or amine. Other such copolymers are copolymers of ethylene and propylene which are grafted with nitrogen compounds.

Representative effective amounts of the antioxidant additives and other additives for providing a lubricant composition according to the disclosure are listed in Table 1 below. All the values listed are stated as weight percent active ingredient.

TABLE 1 Wt. % Wt. % Component (Broad) (Typical) Dispersant 0.5-10.0 1.0-5.0 Oxidation Inhibitors   0-10.0 0.1-6.0 Metal Detergents 0.1-15.0 0.2-8.0 Corrosion Inhibitor  0-5.0   0-2.0 Antifoaming agent  0-5.0 0.001-0.15  Pour point depressant 0.01-5.0  0.01-1.5  Viscosity modifier 0.01-20.00 0.25-10.0 Base oil Balance Balance Total 100 100

Each of the foregoing additives, when used, is used at a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if an additive is a corrosion inhibitor, a functionally effective amount of this corrosion inhibitor would be an amount sufficient to impart the desired corrosion inhibition characteristics to the lubricant. Generally, the concentration of each of these additives, when used, ranges up to about 20% by weight based on the weight of the lubricating oil composition, and in one embodiment from about 0.001% to about 20% by weight, and in one embodiment about 0.01% to about 20% by weight based on the weight of the lubricating oil composition.

The additives may be added directly to the lubricating oil composition. In one embodiment, however, an additive package is diluted with a substantially inert, normally liquid organic diluent such as mineral oil, synthetic oil, naphtha, alkylated (e.g. C₁₀ to C₁₃ alkyl) benzene, toluene or xylene to form an additive concentrate. The concentrates usually contain from about 1% to about 100% by weight and in one embodiment about 10% to about 90% by weight of the additive mixture.

Base Oils

Base oils suitable for use in formulating the compositions, additives and concentrates described herein may be selected from any of the synthetic or natural oils or mixtures thereof. The synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha-olefins, including polybutenes, alkyl benzenes, organic esters of phosphoric acids, polysilicone oils, and alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, and the like.

Lubricating base oils may also include oils made from a waxy feed. The waxy feed may comprise at least 40 weight percent n-paraffins, for example greater than 50 weight percent n-paraffins, and more desirably greater than 75 weight percent n-paraffins. The waxy feed may be a conventional petroleum derived feed, such as, for example, slack wax, or it may be derived from a synthetic feed, such as, for example, a feed prepared from a Fischer-Tropsch synthesis.

Natural base oils include animal oils and vegetable oils (e.g., castor oil, lard oil), liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. Base oil mixtures typically have a viscosity of about 2.5 to about 15 cSt and preferably about 2.5 to about 11 cSt at 100° C.

Among other advantages, the additives and compositions disclosed herein may provide improved lead uptake performance on diesel engines operated on bio-diesel fuels as compared to the same engines using the same lubricants and additives operated on non-biodiesel fuels. Bio-diesel fuels are typically fatty acid ethyl or methyl esters derived animal fats and from edible or non-edible vegetable oils such as, but not limited to, canola, sunflower, rapeseed, soyabean, linseed, and palm oils. Such biodiesel fueled engines may include EGR engines cooled by the circulation or heat exchange of water, water/hydrocarbon blends or mixtures, water/glycol mixtures, and/or air or gas.

Advantages of the embodiments of the disclosure may be further illustrated by the following non-limiting examples. In the examples, all blends were for 20 W-40 grade lubricants. Group I and Group II oils were used as the base oils. The Group I oils were a mixture of VALERO 165 SN and VALERO 700 SN base stocks with a weight ratio of 31:69 wt./wt. The Group II oils were a mixture of CHEVRON RLOP 220 SN and CHEVRON 600 SN base stocks with a weight ratio of 28:72 wt./wt. %. Soluble copper was added to provide 20 ppm copper from copper naphthenate containing 5000 ppm copper.

The oils were evaluated for oxidation protection and lead uptake using a variation of a High Temperature Corrosion Bench Test (HTCBT) according to ASTM D 6594. The modified HTCBT test involves 100 ml of test oil in an ASTM D 943 tube and condenser to retain volatiles. The oil was heated for 168 hours in an oil bath at 135° C., with an air flow of 5 l/hr and four 1 in² each of lead, copper, tin and phosphor bronze metallic coupons wired together at the end of the dip tube acting as oxidation catalysts as well as to measure the corrosive effects of the used oxidized oil. The small variations in test apparatus were checked against actual ASTM D 6594 procedure at two independent outside labs and the all three results on a given oil were found to be comparable and repeatable. Using the D 943 apparatus instead of the more complex D 6594 glassware greatly simplified the test and allowed more tests to be run in a standard oil bath. One milliliter samples of the oils were analyzed for lead, copper and tin by ICP usually every 24 test hours. The formulation of each blended oil is summarized in the following tables.

In the following examples, a base additive formulation containing the aforementioned detergents, dispersants, corrosion inhibitors and antiwear components was combined with a non-dispersant viscosity index improver and the Group I or Group II oil mixture described above. In samples B, C, and E, the alkylene group of the bis-aminotriazole was a 1300 number average molecular weight (MW) highly reactive polyisobutylene group (hereinafter “HR PIB”). Samples A and B are reference oils containing a widely used commercial MSD additive package. The results are shown in FIG. 1.

TABLE 3 Test Lubricant Formulations Sample Sample Sample Sample Sample A B C D E Component (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) Reference Additive 12.04 12.04 — — — Base Additive — — 8.93 8.93 8.93 Copper additive —  0.40 — — 0.40 (5000 ppm) Viscosity Index Improver  3.80  3.80 3.80 3.80 3.80 Group I base oil 84.16 83.76 87.27  — 87.27  Group II base oil — — — 87.27  —

TABLE 4 Lead Uptake and FTIR Results Sample B Sample A Commercial Oil Sample C Sample D Sample E Commercial Reference + 1300 MW HR 1300 MW HR 1300 MW HR Reference Oil Cu(II) PIB PIB PIB + Cu (II) Group I Group I Group II Group I Group I Test Hours Lead (ppm) Lead (ppm) Lead (ppm) Lead (ppm) Lead (ppm)  0 0 0 0 0 0  24 0 0 1  48 45 52 1 4 52  72 1 0 318  96 73 82 1 1 798 120 1 40 1460 144 90 98 1 206 2090 168 95 99 1 405 2680 192 96 111 1 735 3280 216 111 178 1 1100 3860 240 124 502 24 1560 4620 264 229 954 110 1940 5170 288 433 1580 261 5900 312 767 2470 427 6550 336 1270 3670 624 FTIR 1774 168 hrs 2.2 3.0 1.1 4.3 8.1 FTIR 1710 168 hrs 9.2 12.0 4.0 16.1 23.8 FTIR 1704 168 hrs 8.3 10.8 3.3 14.3 21.2 FTIR 1774 EOT 13.9 22.0 3.3 7.5 13.0 FTIR 1710 EOT 34.1 49.8 8.2 22.0 31.1 FTIR 1704 EOT 30.1 43.0 7.0 19.8 27.4

As shown in FIG. 1 and Table 4, the lead uptake and oxidation response of the lubricant formulations containing the base additive composition and the 1300 MW HR PIB bis-aminotriazole in the Group I base oil (Sample D) and in the Group II base oil (Sample C) had significant lead uptake values. The 264 hour (11 day) Group I base oil formulation lead uptake differed by a factor of about eight from the reference oil, even though the FTIR carbonyl absorptions of the two oils differed by less than a factor of two at 168 hours and at end-of-test.

The Group II base oil formulations showed a much smaller magnitude of lead uptake. For example, the worst lead uptake for the 1300 MW HR PIB bis-aminotriazole in the Group II base oil (Sample C) had lower lead uptake at 336 hours (14 days) than the best lead uptake for 1300 MW HR PIB bis-aminotriazole in the Group I base oil (Sample D) after 264 hours (11 days). The lead uptakes of the bis-aminotriazole oil formulations were <10 ppm for the first 9 days of testing and only began to increase on day 10. The FTIR oxidation values of the Group II blends were all very small considering the test time was more than doubled.

Because the differences between the bis-aminotriazole formulation in Group I base oil was dramatically larger than the same formulation in Group II base oil as well as the reference oil in Group I base oil as detailed above, it is believed that the base additive formulations in Group I stocks will require additional components to extend low lead uptake times and increase oil oxidation protection.

In the following examples, the effects of added copper (II) ions on additive formulations in Group I base oil was determined wherein the additives contained 1300 MW HR PIB groups. The lead uptake and oxidation response of formulations containing 1300 MW HR PIB (Sample D) in Group I base oils without 20 ppm soluble copper (II) and the same formulation (Sample E) with soluble copper (II) are also shown in FIG. 1, along with a reference additive blend in the Group I base oils without soluble copper (Sample A) and with soluble copper (Sample B) for comparison. The formulations tested are given in Table 3.

As shown in Table 4, the addition of the 20 ppm copper (II) roughly triples the long-term lead uptake of the formulations using 1300 MW HR PIB bis-aminotriazole (Sample E) compared to the same formulation (Sample D) without soluble copper. The reference additive formulations (A and B) showed the best lead protection with or without the copper.

FIG. 1 also shows a more detailed lead uptake performance for the foregoing samples. Sample A without added copper showed lead uptake under 125 ppm for 240 hours (10 days) before losing protection and the lead uptake rising sharply. When the copper (II) was added to the reference additive formulation (Sample B), the lead protection was reduced to 192 hours (8 days) before the lead uptake rose sharply. None of the Group I additive formulations containing HR PIB bis-aminotriazole showed lead uptake even close to that of the references additive samples A and B. The 1300 MW HR PIB bis-aminotriazole (Sample D) lost lead protection after 5 days. Addition of soluble copper (II) shortened this time to 2 days (Sample E). Accordingly, without more, the base additive formulation with bis-aminotriazole is not expected to provide suitable lead protection in Group I base oils that is comparable to the lead protection of the reference additive in Group I base oils with added copper (II) ions (Sample B).

Based on the foregoing results, the base additive formulation needed additional lead protection and/or oxidation protection to be effective in Group I stocks with soluble copper. In the next series of samples, the lead uptake and oxidation response of base additive formulations containing bis-aminotriazoles and 1.5% by weight antioxidant additive selected from hydroxy phenyl acids and hydroxy phenyl esters as described above in the Group I base oils with and without added copper (II) was determined. For the purposes of this example, Antioxidant 1 is a C₇ to C₉ ester of di-tertiary alkyl hydroxyphenylpropionic acid and Antioxidant 2 is a di-tertiary alkyl hydroxyphenylpropionic acid wherein the alkyl group is a tertiary butyl group. FIG. 2 shows the long-term lead uptake of the base additive formulation containing Antioxidants 1 and 2, both with copper compared with the reference additive formulation with and without copper.

TABLE 5 Test Lubricant Formulations Sample F Sample G Sample H Sample I Component (wt. %) (wt. %) (wt. %) (wt. %) Reference — — — — Additive Base Additive 8.93 8.93 8.93 8.93 Copper additive — 0.40 — 0.40 (5000 ppm) Antioxidant 1 1.50 1.50 — — Antioxidant 2 — — 1.50 1.50 Viscosity Index Improver 3.80 3.80 3.80 3.80 Group I base oil 85.77  85.37  85.77  85.37 

TABLE 6 Lead Uptake and FTIR Results with and without Antioxidant 1 Sample A Sample B Commercial Commercial Oil Oil Sample F Sample G Sample H Sample I Reference Reference + 1300 MW 1300 MW + 1300 MW 1300 MW + No Cu(II) Cu(II) No Cu(II) Cu(II) No Cu(II) Cu(II) Antioxidant 1 — — 1.5 wt. % 1.5 wt. % — — Antioxidant 2 — — — — 1.5 wt. % 1.5 wt. % Test Hours Lead (ppm) Lead (ppm) Lead (ppm) Lead (ppm) Lead (ppm) Lead (ppm)  0 0 0 0 0 0 0  24  48 45 52 0 1 37 50  72  96 73 82 1 1 54 57 120 144 90 98 1 1 66 62 168 95 99 1 1 70 64 192 96 111 7 4 79 68 216 111 178 1 1 85 70 240 124 502 0 2 102 87 264 229 954 2 4 115 105 288 433 1580 3 75 132 126 312 767 2470 4 229 150 150 336 1270 3670 82 515 173 184 360 2010 5420 217 1100 205 237 384 2860 7250 336 1810 230 307 FTIR 1774 168 hrs 2.2 3.0 0.6 1.1 2.1 2.6 FTIR 1710 168 hrs 9.2 12.0 7.4 8.8 3.0 4.0 FTIR 1704 168 hrs 8.3 10.8 5.5 7.1 2.0 3.0 FTIR 1774 EOT 13.9 22.0 7.3 11.5 6.9 9.8 FTIR 1710 EOT 34.1 49.8 23.0 30.4 14.4 20.8 FTIR 1704 EOT 30.1 43.0 20.2 26.6 12.5 18.3

FIG. 2 and Table 6 show that lubricant formulations containing 1.5% by weight of Antioxidant 1 and 20 ppm soluble copper (II) (Sample G) was superior in long-term lead protection to the formulations containing the reference additive with or without copper (Samples A and B). The lubricant formulation containing 1300 MW conventional bis-aminotriazole and Antioxidant 1 without copper (II) (Sample F) is shown for comparison purposes and was the better than the reference additive formulations (Samples A and B) or the formulation with copper (II) (Sample G).

FIG. 2 also shows the reference additive formulation without added copper (Sample A) lasted about 10 days before losing lead uptake control and about 8 days (Sample B) when copper is added. The lead protection of the base additive formulations with 1.5% by weight Antioxidant 1 lasted 12-13 days with 20 ppm added soluble copper (II) (Sample G) which was significantly better than the reference oil formulation (Sample B). Use of 1.5% by weight of the Antioxidant 1 greatly decreased the lead uptake in the Group I lubricant formulation, regardless of the type of bis-aminotriazole used, compared to the same formulations without the Antioxidant 1. Accordingly, the time for lubricant formulations containing Antioxidant 1 to reach a lead uptake value of about 100 ppm was extended from about 50 hours to about 290 hours compared to 170 hours for the reference additive formulation. The results with Antioxidant 1 were surprising and quite unexpected in view of the base oil formulation devoid of Antioxidant 1 that was significantly inferior in lead uptake protection compared to the reference additive formulations (A and B).

In another series of tests, Antioxidant 2 and defined above was used instead of Antioxidant 1 and the lead uptake of the lubricant formulations was determined. The lead uptake and oxidation response of the base additive formulations containing 1300 MW conventional bis-aminotriazole with 1.5% by weight Antioxidant 2 in the Group I base oil without added copper (II) (Sample H) and with added copper (II) (Sample I) was determined. FIG. 2 also shows the long-term lead uptake of the formulations listed in Table 6 with and without added copper along with the reference additive formulation with and without copper.

Antioxidant 2 in the base additive formulation (Sample I) appears to protect lead better in the presence of added copper after 300 test hours than does Antioxidant 1. The difference in lead uptake between Samples H and I at 384 test hours with and without added copper was only 77 ppm (307 versus 230). With the Antioxidant 1, the difference between Samples F and G using 1300 MW conventional bis-aminotriazole with and without added copper was 1474 ppm (1810 versus 336). By comparison, the lead uptake of the reference additive formulations (Sample A and B) with and without added copper was 7250 ppm and 2860 ppm.

Antioxidant 2 may be acting by a different or by an additional mechanism in reducing lead uptake compared to Antioxidant 1. FIG. 2 also shows that the formulations containing Antioxidant 1 (Samples F and G) had lead uptakes that were essentially zero until about 264-312 test hours when the lead uptake rose sharply at a rate of several hundred ppm lead per day. By contrast, the formulations containing Antioxidant 2 (Samples H and I) had a steady rise of lead uptake for the first 100 hours to about 60 ppm lead. The lead uptake for Samples H and I leveled off somewhat for another 100 hours between 60-80 ppm lead, and then slowly rose in an almost linear fashion by about 25 ppm lead per day. The lead uptake curves for Samples H and I almost parallel those of the reference additive formulation, but at 40 ppm less lead at a given time. Where the reference additive formulation with added copper lost lead protection at about 216 hours (9 days), the Samples H and I containing Antioxidant 2 remained in an acceptable lead uptake zone after 264 hours (11 days).

Without desiring to be bound by theoretical considerations, the mechanism of action of Antioxidants 1 and 2 may be that of oxidation control by virtue of their hindered phenolic structure because of the long-term low lead uptake and the moderate FTIR carbonyl values. Nevertheless, formulations containing either antioxidant had similar lead uptake and oxidation values and were relatively insensitive to the presence of the 20 ppm added copper (II) even when the test time was doubled. Accordingly, it is believed that the antioxidant additives of the embodiments of the disclosure are effective to provide increased drain intervals for Group I and Group II oils even in the presence of copper (II) ions.

At numerous places throughout this specification, reference has been made to a number of U.S. Patents. All such cited documents are expressly incorporated in full into this disclosure as if fully set forth herein.

The foregoing embodiments are susceptible to considerable variation in its practice. Accordingly, the embodiments are not intended to be limited to the specific exemplifications set forth hereinabove. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including the equivalents thereof available as a matter of law.

The patentees do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents. 

1. A lubricant composition for a diesel engine comprising: a major amount of oil of lubricating viscosity; a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition; and a minor amount of an antioxidant additive selected from the group consisting essentially of hydroxy phenyl acids and hydroxy phenyl esters of the formula:

wherein each R¹ is a primary, secondary or tertiary alkyl group having from 3 to 6 carbon atoms and R² is selected from the group consisting essentially of C₃ to C₆ acids and C₇ to C₉ esters of the C₃ to C₆ acids, and wherein the lubricant composition is substantially devoid of zinc dialkyldithiophosphate compounds.
 2. The lubricant composition of claim 1, wherein the antioxidant additive comprises di-tertiary alkyl hydroxyphenylpropionic acid.
 3. The lubricant composition of claim 1, wherein the antioxidant additive comprises C₇ to C₉ ester of di-tertiary alkyl hydroxyphenylpropionic acid.
 4. The lubricant composition of claim 1, further comprising a triazole compound.
 5. The lubricant composition of claim 4, wherein the triazole compound is selected from the group consisting essentially of aminotriazole and hydrocarbyl substituted bis-aminotriazoles.
 6. The lubricant composition of claim 5, wherein the triazole compound comprises alkyl bis-1,2,4-triazole-3-amine.
 7. The lubricant composition of claim 6, wherein the alkyl group of the alkyl bis-1,2,4-triazole-3-amine comprises polyisobutylene having greater than about 50 weight percent terminal vinylidene content.
 8. An additive concentrate for a diesel engine lubricant composition comprising: a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the additive concentrate; and an antioxidant selected from the group consisting essentially of hydroxy phenyl acids and hydroxy phenyl esters of the formula:

wherein each R¹ is a primary, secondary or tertiary alkyl group having from 3 to 6 carbon atoms and R² is selected from the group consisting essentially of C₃ to C₆ acids and C₇ to C₉ esters of the C₃ to C₆ acids, and wherein a lubricant composition comprising the additive concentrate is substantially devoid of zinc dialkyldithiophosphate compounds.
 9. The additive concentrate of claim 8, wherein the antioxidant additive comprises di-tertiary alkyl hydroxyphenylpropionic acid.
 10. The additive concentrate of claim 8, wherein the antioxidant additive comprises C₇ to C₉ ester of di-tertiary alkyl hydroxyphenylpropionic acid.
 11. The additive concentrate of claim 8, further comprising a triazole compound.
 12. The additive concentrate of claim 11, wherein the triazole compound is selected from the group consisting essentially of aminotriazole and hydrocarbyl substituted bis-aminotriazoles.
 13. The additive concentrate of claim 12, wherein the triazole compound comprises alkyl bis-1,2,4-triazole-3-amine.
 13. The additive concentrate claim 13, wherein the alkyl group of the alkyl bis 1,2,4-triazole-3-amine comprises polyisobutylene having greater than about 50 weight percent terminal vinylidene content.
 14. A method for extending the drain interval for a lubricant for a medium speed diesel engine comprising: supplying as the lubricant, a lubricant composition comprising a sulfonate detergent and a phenate detergent, wherein the phenate detergent is present in an amount that is greater than 15 percent by weight of the total weight of detergents in the lubricant composition; and an antioxidant selected from the group consisting essentially of hindered phenolic derivatives of C₃ to C₆ acids and C₇ to C₉ esters of hindered phenolic derivatives of C₃ to C₆ acids, wherein the lubricant composition is substantially devoid of zinc dialkydithiophosphate compounds; and operating the engine on the lubricant composition for an extended period of time between lubricant drain intervals.
 15. The method of claim 14 wherein the antioxidant comprises a compound of the formula:

wherein each R¹ is a primary, secondary or tertiary alkyl group having from 3 to 6 carbon atoms and R² is selected from the group consisting essentially of C₃ to C₆ acids and C₇ to C₉ esters of the C₃ to C₆ acids.
 16. The method of claim 14, wherein the antioxidant comprises di-tertiary alkyl hydroxyphenylpropionic acid.
 17. The method of claim 14, wherein the antioxidant additive comprises C₇ to C₉ ester of di-tertiary alkyl hydroxyphenylpropionic acid.
 18. The method of claim 14, wherein the lubricant composition further comprises a triazole compound.
 19. The method of claim 18, wherein the triazole compound is selected from the group consisting essentially of aminotriazole and hydrocarbyl substituted bis-aminotriazoles.
 20. The method of claim 19, wherein the triazole compound comprises alkyl bis-1,2,4-triazole-3-amine.
 21. The method of claim 20, wherein the alkyl group of the alkyl bis 1,2,4-triazole-3-amine comprises polyisobutylene having greater than about 50 weight percent terminal vinylidene content.
 22. The method of claim 14, wherein the extended period of time is greater than about 200 days between drain intervals.
 23. The method of claim 14, wherein the extended period of time is greater than about 250 days between drain intervals.
 24. The method of claim 14, wherein the medium speed diesel engine is operated on a biodiesel fuel. 